Limonene, pinene, or other terpenes and their alcohols, aldehydes and ketones, as polymer solvents for conducting polymers in aqueous and non-aqueous coating formulations and their uses

ABSTRACT

A low-VOC (volatile organic compound) and/or low-toxicity coating formulation, including at least one non-halogenated solvent including terpene(s) or terpenoid(s), and at least one polymer including conducting polymers, electroactive polymers and/or conjugated polymers, wherein the polymers and non-halogenated solvent(s) are in non-aqueous form. In other embodiments, coating formulations, includes about 0.01% wt. to about 99.9% wt. of at least one non-halogenated solvent including a terpene or terpenoid, about 0.01% wt. to about 90% wt. of at least one polymer including conducting polymers, conjugated polymers, and electroactive polymers, and about 0.001% wt to about 90% wt. of at least one surfactant, wherein the polymers, solvents, and surfactants are in non-aqueous form. Also included are aqueous low VOC and/or toxicity coating formulations having at least one non-halogenated solvent including terpene(s) or terpenoid(s), and at least one conjugated, electroactive, or conductive polymer, copolymer, block polymer, and mixtures thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119(e) and is acontinuation-in-part of U.S. patent application Ser. No. 10/714,296filed Nov. 14, 2003, and is hereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The invention described herein may be manufactured and used by or forthe government of the United States of America for governmental purposeswithout the payment of any royalties thereon or therefor.

FIELD OF THE INVENTION

The present invention relates to coating formulations including terpenesor terpenoids and their alcohols as solvents with conducting polymers,and more specifically, the use of terpenes to permit polymerincorporation into non-toxic or low-toxicity, non-VOC (Volatile OrganicCarbons) or low-VOC aqueous and non-aqueous formulations for variousmilitary, commercial, and recreational applications.

BACKGROUND OF THE INVENTION

Terpenes are natural solvents existing both in the citrus fruits and inmany other plants, with extraordinary technical and chemical properties.Terpenes include any hydrocarbon of the formula C₅H₈ and are derivablechiefly from essential oils, resins, and other vegetable aromaticproducts. Many terpenes are acyclic, bicyclic, or monocyclic, and differsomewhat in physical properties. They can represent an optimalalternative to halogenated solvents in many civil and industrialapplications.

Nearly all the terpenes, contained in the essential oils of many plants,are constituted by a skeleton of carbon atoms made of isoprene (C₅H₈)units regularly linked according with the head-tail position. Somecomponents are shown in the following formulas. The main component ofthe essential citrus fruit oil is d-limonene, commonly called dipentene,a hydrocarbon insoluble in water. When the essential oils are used toflavor something, it's necessary to bring them in a very thin suspensionin the aqueous product (soft drinks, juices, etc.). Terpenes aretypically environmentally safe and can reduce the environmental impactin many applications related to the organic solvent use.

U.S. Pat. No. 5,814,376 issued on Sep. 29, 1998 to Michael D. Cabelliteaches a gravure coating process for producing electroconductivepolymer films. The coating is for use in sensors detecting analytes andthe final product is heated. The above patent is limited to aribbon-like or flat substrate application. The above uses a conductivepolymer and exposing it to a dopant thereby changing its properties insitu. By changing it's properties they teach that it can be used as acomponent in a measuring device. This patent does not teach the use ofterpenes with conductive polymers for corrosion inhibition. Ideally, inthe present invention, once used or applied, the polymer will not bechanged, modified or doped. The polymer will continue to perform(prevent corrosion) if it remains in a constant state. While the detailsof the mechanism for corrosion protection/inhibition has not beenpublished for conductive polymers, it is likely to be a passivation ofthe metal substrate or an ability to allow electron transfer between thecoating and substrate to prevent localized charge buildup at a metalsurface, thereby eliminating corrosion. By preventing a localized chargebuildup at a metal surface or between two surfaces that have differentoxidation potentials, it's likely that the conductive polymer inhibitsthe oxidation of metal and therefore the formation of corrosionproducts.

U.S. Pat. No. 5,932,643 issued on Aug. 3, 1999 to Frank J. Kenny teachescoating formulations and thermal transfer ribbons that form printedimages containing conductive polymers. The formulations and ribbonsinclude wax, polymer resins, a sensible material and optional solvent.The above is teaching the polymer coatings for their thermal transferproperties. They teach utilizing toxic organic solvents, which have beenused for conductive polymers long before this patent was issued.However, no terpenes or terpenoids are taught for use in this patent.

If paint formulations use limonene, pinene, or other terpenes (orterpenoids), as a solvent in a non-water based coating applicationsinstead of traditional high-VOC (volatile organic compound) solvents, itwill provide a low-VOC coating application. There is currently nonon-toxic, non-chrome, non-metallic, non-aqueous containing coatingformulation approved for military application. From the foregoing, itwill be appreciated that there is a need in the art for organic terpenenon-aqueous based solvent/conducting polymer coating compositions, whichis environmentally safe for various types of military and commercialapplications. The present invention is directed to overcoming one, ormore, of the problems set forth above.

SUMMARY OF THE INVENTION

The present invention relates to low-VOC (volatile organic compound)and/or low-toxicity coating formulations, including at least onenon-halogenated solvent including terpene(s) or terpenoid(s) and atleast one polymer comprising one of conducting polymers, electroactivepolymers and/or conjugated polymers, wherein the non-halogenatedsolvent(s) and polymer(s) are in non-aqueous form. In anotherembodiment, the present invention includes a low-VOC (volatile organiccompound) and/or low-toxicity coating formulation, including about 0.01%wt. to about 99.9% wt. of at least one non-halogenated solvent includingterpene(s) or terpenoid(s), about 0.01% wt. to about 90% wt. of at leastone polymer comprising of conducting or electroactive polymer(s),conjugated polymer(s), and about 0.001% wt to about 90% wt. of at leastone surfactant, wherein non-halogenated solvent(s), polymer(s), andsurfactant(s) are in non-aqueous form. In other embodiments, the coatingformulations include at least one of co-polymer, block polymer, andmixtures thereof. Embodiments of the present invention further includeaqueous low VOC and/or toxicity coating formulations having at least onenon-halogenated solvent including terpene(s) or terpenoid(s), and atleast one copolymer, block polymer, and mixtures thereof.

The terpene or terpenoid includes at least one of dipentene(d-limonene), α-pinene, β-mircene, p-cimene, citronellolio, geraniale(citrale), nerol, beta-carotene, menthol, geraniol, farnesol, phytol,their homologs, derivative, enantiomers, isomers includingconstitutional isomers, stereoisomerisms, regioisomers, and geometricisomers, and any combination thereof. The conducting polymers include atleast one of poly dialkylaminophenylene vinylene includingpoly[bis(N-methyl-N-hexylamino)phenylenevinylene] (BAMPPV) andpolydialkoxyphenylenevinylene includingpoly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV),polyphenylene vinylenes, polythiophenes, polypyrroles, polyanilines,polyacetates, polyacetylenes, polyacrylates, polyazene, polystyrene,poly-N-vinylcarbazole, polyvinylpyridine, polyindole, copolymer, blockpolymer, and any combination thereof. The conducting (includingelectroactive or conjugated) polymers are in neutral, oxidized orreduced form, in the form of a salt including an emeraldine salt, or inany basic or acidic form.

The present invention is used with a broader range of applicationmethods, particularly, spray coating and dip coating. These methods arethe most useful for industry and the military on large substrates andsubstrates with complex geometries (crevices or holes that are hard toaccess) including aircraft and vehicle components.

It is to be understood that the foregoing general description and thefollowing detailed description are exemplary and explanatory only andare not to be viewed as being restrictive of the present invention, asclaimed. These and other objects, features and advantages of the presentinvention will become apparent after a review of the following detaileddescription of the disclosed embodiments and the appended claims.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

The present invention relates to low-VOC (volatile organic compound)and/or low-toxicity coating formulations, including at least onenon-halogenated solvent including terpene(s) or terpenoid(s) and atleast one polymer comprising of conducting polymer(s), electroactivepolymer(s) and/or conjugated polymer(s), wherein the non-halogenatedsolvent(s) and the polymer(s) are in non-aqueous form. In anotherembodiment, the present invention includes a low-VOC (volatile organiccompound) and/or low-toxicity coating formulation, including about 0.01%wt. to about 99.9% wt. of at least one non-halogenated solvent includingterpene(s) or terpenoid(s), about 0.01% wt. to about 90% wt. of at leastone polymer comprising of conducting polymer(s), electroactivepolymer(s), and conjugated polymer(s), and about 0.001% wt to about 90%wt. of at least one surfactant, wherein the non-halogenated solvent(s),polymer(s) and surfactant(s) are in non-aqueous form. In otherembodiments of the present invention, the coating formulations includeat least one of copolymers, block polymers, and mixtures thereof.

The following terpenes or terpenoids are constituted by a skeleton ofcarbon atoms made of isoprene unities regularly linked according withthe head-tail position. The terpene or terpenoid includes at least oneof dipentene (d-limonene), α-pinene, β-mircene, p-cimene, citronellolio,geraniale (citrale), nerol, beta-carotene, menthol, geraniol, farnesol,phytol, their homologs, derivative, enantiomers, isomers includingconstitutional isomers, stereoisomerisms, regioisomers, and geometricisomers, and any combination thereof. For example, Aldrich produceslimonene in various optically active isomers and in a technical gradecalled “dipentene.” Terpenes also function as stand-alone solvents or asco solvents. As a solvent or co solvent, a terpene will act as a vehiclefor application of polymers (conductive or nonconductive) or conjugatedpolymers onto substrates. Terpenes function as alternative solvents forpolymers, including conductive or electroactive polymers and conjugatedpolymers, to replace more traditional, more toxic solvents including butnot limited to xylenes, tetrahydrofuran (THF), benzene,n-methylpyrrolidinone (NMP), methylene chloride, and other organicsolvents.

Conjugated polymers have a framework of alternating single and doublebonds. These consist of carbon hetero-atom bonds including but notlimited to carbon—carbon, carbon-nitrogen, carbon-oxygen, carbon-sulphurbonds. Conjugated polymers are polyunsaturated compounds in which mostif not all backbone atoms are sp- or sp²-hybridized. For the purposes ofthe present invention, the terms conductive, electroactive, andconjugated will be interchangeably utilized throughout. For the purposesof the present invention, a conductive polymer may include homopolymers,block polymers, copolymers, or mixtures thereof. The conducting polymersinclude at least one of polydialkylaminophenylenevinylene includingpoly[bis(N-methyl-N-hexylamino)phenylenevinylene] (BAMPPV) andpolydialkoxyphenylenevinylene includingpoly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV),polyphenylene vinylenes, polythiophenes, polypyrroles, polyanilines,polyacetates, polyacetylenes, polyacrylates, polyazene, polystyrene,poly-N-vinylcarbazole, polyvinylpyridine, polyindole, and anycombination thereof. The conducting (including electroactive orconjugated) polymers are in neutral, oxidized or reduced form, in theform of a salt including an emeraldine salt, or in any basic or acidicform. The terpene or terpenoid solvent and conducting polymerformulations are in non-aqueous form comprising a solution, mixture,suspension, or emulsion. All terpenes, terpenoids, and polymers wouldideally be non/low toxic and low VOC.

In other embodiments the coating formulations further include at leastone of surfactant(s), solvent(s), either organic or inorganic, and otherorganic components. Triton X100 is a surfactant utilized in embodimentsof the present invention; however, any surfactant commercially availablewill suffice that includes the following characteristics. The definitionof a surfactant or surface-active agent (Random House) is “any substancethat when dissolved in water or other aqueous solution reduces thesurface tension or interfacial tension between it and another fluid.” Asurfactant is utilized with non-aqueous systems, for example, a solventhaving a non-aqueous (pure) alcohol including ethanol, methanol, orpropanol that have polar characteristics like water. The idea of asurfactant is to have different functionalities on the same molecule.This will enable two different types of molecules to be somehow somewhatmiscible that normally would not be. The Triton X100 has a similarstructure (carbon ring) to the polymer and the ether alcohol portion issimilar to water (polar) so that the water and polymer may be somehowclosely associated to form a suspension or solution rather thanseparating into two layers like oil and water.

In embodiments of the present invention, terpene and polymer solutions,mixtures, suspensions, or emulsions are added to organic coatingsystems. Above combinations are used to incorporate a polymer into anorganic or inorganic coating or resin, including but not limited toepoxies, polyurethanes, polyamides, polyimides, polysulfides,polysiloxanes, polyvinyls, polyphenolics, polyxylenes, polyacrylics andpolyesters. In embodiments of the present invention, organic resinincludes, but is not limited to polyamides, phenolics, polypropylenes,and polyethylenes. The present coating formulations can be applied to asubstrate including, but not limited to spray coating, dip coating,spin-coating, flow-coating, doctor blade coating, or screen-printing.The substrates include plastic, rubber, metal, metallic and likesurfaces. Embodiments of the present invention are further utilized forcorrosion protection as replacements for hexavalent chrome.

The present invention will now be explained with references to thefollowing non-limiting experiments.

Experimental Results

The following experiments are based on aqueous coating formulations. Aseries of terpene polymer solvent samples were prepared and analyzed. Inthe first experiment, approximately 5.6 mL of dipentene (d-limonene)(Aldrich) was added to beaker “A” with 0.0112 g ofpoly[bis(2,5-(N,N,N′,N′-tetraalkyl)amino)-1,4-phenylene vinylene](BAMPPV). The results had shown that BAMPPV was slightly soluble almostimmediately in the dipentene. The terpene/BAMPPV mixture was stirred andwarmed on low. The BAMPPV polymer was solubilized in solution after 25minutes.

In the second experiment, approximately 5.6 mL of α-pinene (Aldrich) wasadded to beaker “B” with 0.0103 g of BAMPPV. The results shown that theBAMPPV polymer was not immediately soluble in the α-pinene terpene as inthe first experiment utilizing dipentene. The dipentene/BAMPPV andα-pinene/BAMPPV solutions were separately allowed to stir overnight. Inthe first experiment, the BAMPPV was completely dissolved in thedipentene solvent. In the second experiment, the BAMPPV was almostcompletely dissolved in the α-pinene solvent; however, a small amount ofsolids remained. These experiments have shown that the solubility of theBAMPPV polymer in α-pinene is far greater than in xylenes and THF.Previous solutions trying to dissolve xylenes and THF into a BAMPPV (theBAMPPV was dissolved in the xylenes and THF) polymer batch had shown asolubility factor not greater than 0.01% (order of magnitudedifference).

In the second experiment, 1 mL of water was further added to beaker “B”containing the α-pinene/BAMPPV solution and was stirred to form asuspension. Water was added in order to form a waterborne coating. Anideal formulation would contain as much polymer as possible (referred toas high solids loading) and as little solvent as possible. Since wateris nontoxic and inexpensive compared to any other solvent(environmentally friendly terpene or not), maximizing the polymercontent, water content and minimizing any organic solvent and surfactantwas the goal in aqueous based coating formulations. In a thirdexperiment, a 1% solution was made with 0.4338 g of BAMPPV and 42.95 gof dipentene. The solution in the third experiment was used for smallertest vial experiments. Smaller tests were done using differentsurfactants to evaluate their respective performance in the coatingformulation. Ideally, a non-toxic surfactant that can give the desiredresults in the smallest quantity possible is the most useful from anenvironmental and economic point of view.

In a fourth experiment, a vial of 9.904 g of dipentene was added to0.1004 g of BAMPPV. The dipentene/BAMPPV solution was further diluted to0.5% by adding 10.33 g of dipentene. A few milliliters of water wereadded to form a suspension. After sitting for an hour, a separation wasobserved. Then 2 drops of Triton-X100 (a surfactant) was added and themixture was stirred for approximately 1 minute and an excellentsuspension resulted. The composition remained in a suspension for a fewdays. After one week, separation was observed. Upon mixing the solutionagain for a few minutes, the suspension was again observed. The vial wasthen allowed to sit without stirring. The suspension was observed to bestable for at least 5 hours. Due to the concentrations of water andweight of Triton-X100 not being precisely measured, this experimentneeded to be repeated.

In the fifth and sixth experiments, compositions including BAMPPV indipentene were added with different surfactants to observe thesurfactant performance. The surfactants were obtained from OsiSpecialties (Greenwich, Conn.) including A1100(gamma-aminopropyltriethoxysilane), A 1101(gamma-aminopropyltriethoxysilane) technical grade, A1170(bis-(gamma-triethoxysilypropyl)amine), and Y9669(n-phenyl-gamma-aminopropyltrimethoxysilane). These additionalsurfactants were compared to the Triton-X100 (polyoxyethylene (10)isooctylcyclohexylether also known as alkylaryl polyether alcohol).

Further experiments were also performed to determine terpene use withconducting polymers. Vial 1: 44.0170 g of dipentene was added to 0.4408g of polymer for a 1% solution. Vial 2: 16.9421 g of dipentene was addedto 0.3369 g of polymer for a 2% solution. Vial 3: 16.9133 g of dipentenewas added to 0.5076 g of polymer for a 2.9% solution. Vial 4: 4.9960 gof DI water was added to 4.2717 g of the 1% solution. Then 3 drops ofTriton X100 (5 drop=0.0249 g) was added to the vial. After addition of 3drops Triton X100, slight separation was noted at bottom, clearer layeron bottom (not completely clear). Vial 5: 2.0447 g of DI water was addedto 4.3224 g of the 1% solution. Then 1 drop of Triton X (5 drop=0.0249g) was added to the vial. Vial 6: 1.910 g of DI water was added to4.2712 g of the 1% solution. Then 3 drops of Triton X (5 drop=0.0249 g)was added to the vial. Vial 7: 1.9773 g of DI water was added to 4.3381g of the 1% solution. Then 2 drops of Triton X (5 drop=0.0249 g) wasadded to the vial.

The results of the above experiments are as follows: 1%polymer/dipentene solution: 1.0005 g of polymer added to 98.9992 g ofdipentene. Did not go completely into solution when stirred overnight,so heated and let stir overnight again. Vial A: 1.0245 g of water wasadded to 5.0468 g of limonene/polymer solution. 0.2693 g of Triton X100was then added. Vial B: 3.0188 g of water was added to 5.0421 g oflimonene/polymer solution. 0.2630 g of Triton X100 was then added. VialC, 5.0184 g of water was added to 5.0455 g of limonene/solution. 0.2491g of Triton X100 was then added.

Vial D: 0.2462 g of Triton X100 was added to 5.0477 g oflimonene/polymer solution. 1.0349 g of water was added to the limoneneand Triton X100. Vial E: 0.2845 g of Triton X was added to 5.0493 g oflimonene/polymer solution. 3.0154 g of water was added to the limoneneand Triton X100. Vial F: 0.2620 g of Triton X was added to 5.0233 g oflimonene/polymer solution. 5.0168 g of water was added to the limoneneand Triton X100. When adding water after Triton X, a precipitate formedon the bottom of the vial more often than when water was added beforeTriton X. But, after stirring for a while, both group ABC and group DEFstarted to look the same. Vials A and D appeared good, but some initialseparation was noticed in B, C, E, and F.

Additional terpenes and conducting polymers experiments were performedwith the following results. Vial G: 1.7914 g of dipentene was added to0.0200 g of Poly(3-hexylthiophene-2,5-diyl)regiorandom. Vial H, 1.8051 gof pinene was added to 0.0200 g ofPoly(3-hexylthiophene-2,5-diyl)regiorandom. Vial I: 1.8015 g ofdipentene was added to 0.0207 g of MEH-PPV. Vial J: 1.8053 g of pinenewas added to 0.0218 g of MEH-PPV. Vial K: 1.8004 g of dipentene wasadded to 0.0261 g of Poly(3-hexylthiophene-2,5-diyl)regioregular. VialL: 1.8024 g of pinene was added to 0.0226 g ofPoly(3-hexylthiophene-2,5-diyl)regioregular. H and G are fully soluble,K and L are mostly soluble, and I and J are mostly soluble. 24 hourslater, all vials appear in the same condition all the previous day. Thesolutions from vials G through L were filtered with 0.2 micron syringefilters to remove any remaining solids. The solutions were then used inwaterborne formulations. The solutions were filtered into new vials withdesignations 38A, 38B, 38C, 38D, 38E, 38E, and 38F corresponding tovials G, H, I, J, K and L, respectively. One drop of Triton X100 wasadded to each vial and the contents stirred. Visual results were asfollows: 38A was in solution after about 20 seconds. 38B was in solutionafter about 30 seconds. 38C and 38D were in solution after about 25seconds. 38E and 38F were in solution for a few seconds and theseparation occurred. 38A, 38B, 38C and 38D stayed in solution after atotal of 2 drops of Triton X100 was added. After 2 minutes, mixtures of38B and 38D began to separate. After 2 min 30 seconds mixtures 38A and38C began to separate. Optimum ratios and stirring conditions are beingestablished. Embodiments of the present invention further includeaqueous low VOC and/or toxicity coating formulations having at least onenon-halogenated solvent including any terpene or terpenoid, and at leastone conjugated, electroactive, or conductive polymer, copolymer, blockpolymer, and mixtures thereof.

The following experiments of the present invention are based onnon-aqueous coating formulations. Vial M: included 2.5192 g of 1%BAM-PPV in dipentene (by weight). Approximately 1.9450 g of 1-propanolwas then added to Vial M. The vial was shaken vigorously and stirred.The contents of the Vial M were miscible. The contents appeared as atransparent orange-red solution. Additional 1-propanol was added for atotal of 4.3089 g. The vial was again shaken and stirred. The contentswere still miscible. After sitting for approximately 10 minutes, thereappeared to be a slight cloudiness due to a small amount of polymerprecipitation or micelle formation. Any precipitate still appeared to besuspended and the mixture still appeared as a good sprayable material.

Vial N: included 0.0072 g of dry BAM-PPV. Approximately 2.4041 g of1-propanol was then added. Dipentene was added dropwise until 0.6078grams was added. The contents were stirred overnight on low heat. Afterapproximately 15 hours, some of the solids had been dissolved, however,a significant amount of solids remained. After allowing the contents tosit without agitation for over 4 hours, there is a slight amount ofprecipitation seen at the bottom of the vial. Gentle shaking causes theparticles to become suspended again. Vial O: includes 0.5760 g of a 1%solution (by weight) of MEH-PPV in dipentene. Approximately 1.3136 g of1-propanol was then added to the vial and it's contents shakenvigorously and stirred. The contents were slightly cloudy (possiblymicelles). The contents were allowed to stir overnight on low heat.After approximately 15 hours, there was no visible change. The contentsappeared as a very slightly cloudy red liquid. After allowing thecontents to sit without agitation for over 4 hours, there is a slightamount of precipitation seen at the bottom of the vial. Gentle shakingcauses the particles to become suspended again.

Vial P: included 0.9704 g of 1% solution of BAM-PPV in dipentene.Approximately 1.7221 g of 100% ethanol (ethyl alcohol) was then added.The contents were shaken vigorously. The contents were miscible, a redtransparent liquid resulted. Vial Q: included 0.6081 g of MEH-PPV.Approximately 0.6830 g of 100% methanol was then added. An additional0.4596 g of methanol was then added for a total of 1.1426 g of methanol.The contents appeared to be miscible but a slight precipitation orpossible micelle formation may have occurred just after addition wascomplete. The contents appeared to be a very slightly cloudy, redliquid. Vial R: included 0.8612 g of 1% BAM-PPV in dipentene solution.Approximately 0.7146 g of 100% methanol (methyl alcohol) was then added.The contents appeared to be miscible until approximately one half of themethanol was added, at which point the solution became slightly cloudy.After the mixture was allowed to sit with no agitation for approximately10 minutes, a precipitation appeared on the bottom of the vial.Agitation caused the particles to be suspended but precipitationreoccurred. Additional heating and shearing of this or any similarmixtures are likely to increase suspension lifetime.

Embodiments of the present invention are included, but not limited tothe following uses: light-emitting devices, photovoltaic cells,capacitors, super capacitors, devices for sensor protection againstlasers, devices for optical switching and modulating, corrosionprotection, adhesives, electromagnetic shielding (EMI), anti-biofouling,camouflage, chemical sensors. The use of terpenes or terpenoids to actas a solvent or co-solvent will permit the dispersion of a conductingpolymer(s) into a non-aqueous form in solution, suspension, emulsion, ormixture. Embodiments of the present invention including conductivepolymers are used to reduce or inhibit corrosion in organic coatingswhen applied to plastic, rubber, metal substrates, or their interfaces.

Coatings including the present invention terpene/conducting polymerformulations are used as low-VOC (volatile organic compound) and/orlow-toxicity coatings for items including but not limited to aircraft,vehicles, ground equipment, structures and architectural components.Low-VOC coatings are desirable since they should exhibit low-VOCemissions into the atmosphere and reduce hazardous materials exposure tothose personnel that apply, repair, or remove such coatings. Thecoatings of the present invention would be amenable but not limited toapplications on aircraft or ship hardware in compliance with State andFederal environmental regulations.

It should be understood that the examples and embodiments describedherein are for illustrative purposes only and that various modificationsor changes in light thereof will be suggested to persons skilled in theart and are to be included within the spirit and purview of thisapplication and the scope of the appended claims.

1. A coating formulation, comprising: at least one non-halogenatedsolvent including terpene(s) or terpenoid(s); at least one polymerselected from the group of polydialkylaminophenylene vinylenes.
 2. Acoating formulation, comprising: at least one non-halogenated solventincluding terpene(s) or terpenoid(s); at least one polymer selected fromthe group of polydialkyloxyphenylenevinylenes.
 3. The coatingformulation according to claim 1, or claim 2, wherein said terpene orterpenoid comprises at least one such solvent selected from the groupconsisting of dipentene (d-limonene), α-pinene, β-mircene, p-cimene,citronellolio, geraniale (citrale), nerol, beta-carotene, menthol,geraniol, farnesol and phytol.
 4. The coating formulation according toclaim 1, wherein said polymers comprisepoly[bis(N-methyl-N-hexylamino)phenylenevinylene].
 5. The coatingformulation according to claim 1, claim 2, claim 3, or claim 4, furthercomprising at least one of surfactant.
 6. The coating formulationaccording to claim 1, claim 2, claim 3, or claim 4, wherein saidpolymers are in neutral, oxidized or reduced form, in the form of a saltincluding an emeraldine salt, or in any basic or acidic form.
 7. Thecoating formulation according to claim 1, claim 2, claim 3 or claim 4,wherein said solvent and said polymer formulation is a solution,mixture, suspension, or emulsion.
 8. The coating formulation accordingto claim 1, claim 2, claim 3 or claim 4, wherein said polymers comprisea polymer selected from the group consisting ofpoly[bis(N-methyl-N-hexylamino)phenylenevinylene] andpoly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene].
 9. Thecoating formulation according to claim 1, claim 2, claim 3 or claim 4,further comprising at least one polymer selected from the groupconsisting of an epoxy, a polyurethane, a polyamide, a polyimide, apolysulfide, a polysiloxane, a polyvinyl, a polyphenolic, a polyxylene,a polyacrylic and a polyester.
 10. A coating formulation, comprising:about 0.01% wt. to about 99.9% wt. of at least one non-halogenatedsolvent including terpene(s) or terpenoid(s); about 0.01% wt. to about90% wt. of at least one polymer selected from the group ofpolydialkylaminophenylene vinylenes; and about 0.001% wt to about 90%wt. of at least one surfactant.
 11. A coating formulation, comprising:about 0.01% wt. to about 99.9% wt. of at least one non-halogenatedsolvent including terpene(s) or terpenoid(s); about 0.01% wt. to about90% wt. of at least one polymer selected from the group ofpolydialkyloxyphenylenevinylenes; and about 0.001% wt to about 90% wt.of at least one surfactant.
 12. The coating formulation according toclaim 10, or claim 11, wherein said terpene or terpenoid comprises atleast one such solvent selected from the group consisting of dipentene(d-limonene), α-pinene, β-mircene, p-cimene, citronellolio, geraniale(citrale), nerol, beta-carotene, menthol, geraniol, farnesol and phytol.13. The coating formulation according to claim 10, wherein said polymerscomprise poly[bis(N-methyl-N-hexylamino)phenylenevinylene].
 14. Thecoating formulation according to claim 11, wherein said polymerscomprises poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene].15. The coating formulation according to claim 10, or claim 11, whereinsaid polymers are in neutral, oxidized or reduced form, in the form of asalt including an emeraldine salt, or in any basic or acidic form. 16.The coating formulation according to claim 10, or claim 11, wherein saidsolvent and said polymer formulation is a solution, mixture, suspension,or emulsion.
 17. The coating formulation according to claim 10, or claim11, wherein said polymers comprise a polymer selected from the groupconsisting of poly[bis(N-methyl-N-hexylamino)phenylenevinylene] andpoly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene].
 18. Thecoating formulation according to claim 10, or claim 11, furthercomprising at least one polymer selected from the group consisting of anepoxy, a polyurethane, a polyamide, a polyimide, a polysulfide, apolysiloxane, a polyvinyl, a polyphenolic, a polyxylene, a polyacrylicand a polyester.
 19. The coating formulation according to claim 2,wherein said polymers comprisepoly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene].
 20. Thecoating formulation according to claim 19, further comprising at leastone of surfactant.
 21. A composition comprising: one or more solventsselected from the group of terpenes; andpoly[bis(N-methyl-N-hexylamino)phenylenevinylene].
 22. A compositioncomprising: one or more solvents selected from the group of terpinoids;and poly[bis(N-methyl-N-hexylamino)phenylenevinylene].
 23. A compositioncomprising: one or more solvents selected from the group of terpenes;and poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene].
 24. Acomposition comprising: one or more solvents selected from the group ofterpinoids; andpoly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene].
 25. Thecomposition of claim 1, claim 2, claim 4, claim 10, claim 11, claim 19,claim 21, claim 22, claim 23, or claim 24, further comprising water. 26.The coating formulation according to claim 1, claim 2, claim 3, claim 4,claim 10, claim 11, claim 13, claim 14, claim 19, claim 21, claim 22,claim 23 or claim 24 wherein said terpene or terpenoid comprises ahomolog, enantiomer, constitutional isomer, stereoisomer, regioisomer orgeometric isomer of at least one such solvent selected from the groupconsisting of dipentene (d-limonene), α-pinene, β-mircene, p-cimene,citronellolio, geraniale (citrale), nerol, beta-carotene, menthol,geraniol, farnesol and phytol.